A tetrapyridine ligand with a rigid tetrahedral core forms metal-organic frameworks with PtS type architecture

A new tetradentate, pyridine ligand with a rigid tetrahedral core can be prepared in good yield by a cross-coupling methodology. Two metal organic framework structures of Cu(II) with PtS-type topology having a carbon atom as the tetrahedral node have been characterized utilising this ligand.     

Mesoporous titanium phosphate molecular sieves with ion-exchange capacity.

Novel open framework molecular sieves, titanium(IV) phosphates named, i.e., TCM-7 and -8 (Toyota Composite Materials, numbers 7 and 8), with new mesoporous cationic framework topologies obtained by using both cationic and anionic surfactants are reported. The (31)P MAS NMR, UV-visible absorption, and XANES data suggest the tetrahedral state of P and Ti, and stabilization of the tetrahedral state of Ti in TCM-7/8 is due to the incorporation of phosphorus (at Ti/P = 1:1) vis-à-vis the most stable octahedral state of Ti in the pure mesoporous TiO(2). Mesoporous TCM-7 and -8 show anion exchange capacity due to the framework phosphonium cation and cation exchange capacity due to defective P-OH groups. The high catalytic activity in the liquid-phase partial oxidation of cyclohexene with a dilute H(2)O(2) oxidant supports the tetrahedral coordination of Ti in these materials.     

DUAL BEHAVIOR OF ACETONITRILE IN A NEW CADMIUM CYANIDE CLATHRATE: CRYSTAL STRUCTURE OF Cd(CH3CN)2Cd(CN)4·2CH3CN

Abstract

We report a new crystal structure of the title clathrate containing tetrahedral and octahedral Cd atoms in a ratio of 1:1. The preparation of the compound is similar to that of the cristobalite-like clathrate Cd(CN)₂·G, where all Cd atoms are tetrahedral. The new inclusion compound crystallizes in the monoclinic space group C2/c, a = 12.337(4), b = 11.964(3), c = 13.594(3) Å, β = 108.60(2)°, Z = 4, R = 0.034 for 1631 reflections. The three-dimensional host framework is built of alternate linkages between the tetrahedral Cd atom of the tetracyanocadmate and the octahedral Cd atom similar to that of the Hofmann-Td and the en-Td types. In the new clathrate dual behavior of acetonitrile, one as a unidentate ligand in the three-dimensional host framework and the other as the guest in the cage-like cavity, has been demonstrated.     

Interrupted zeolite LTA and ATN-type boron imidazolate frameworks

Zeolite A (LTA) is of much interest in zeolite family because of its large-scale industrial applications. Making Zeolite A (a typical 4-connected tetrahedral framework material) with a lower connectivity (3-connected) might lead to new open architecture with expanded ring size and enhanced functionality. The first interrupted Zeolite A with 3-connected network has been experimentally realized here by a boron imidazolate (im) framework material (BIF-20) with 3-coordinate BH(mim)(3)(-) building units. Additionally, a new strategy toward the construction of functional microporous metal-organic frameworks with interrupted zeolite-type topologies is presented by both 3-connected boron imidazolate frameworks (BIF-20 and BIF-21). BIF-20 has an unusual tetrahedral framework with both debonded α and β cages, and exhibits high H(2) uptake capacity.     

Group 11 metal complexes of SPS-based pincer ligands: syntheses, X-ray structures and reactivity

New group 11 d10 (Cu, Au) metal complexes with SPS pincer ligand were synthesized. Insoluble dimeric or oligomeric complexes [(SP(R)S)Cu](n) (R = Bu:4, Me:5) were readily cleaved by several two-electron donor ligands (phosphines, isocyanides, pyridine) to yield a range of new complexes (6-13). X-Ray crystal studies were performed on complexes 7, 8, 9, 11, which revealed distorted tetrahedral geometries and proved once again the flexibility of the SPS ligand, which can accommodate square planar, tetrahedral, octahedral and trigonal bipyramidal geometries. A dimeric gold species with an Au-Au interaction 16 was also synthesized. This dimer could be cleaved with two electron donor ligand (PPh(3):17, RNC: 18). Reactivity of complex 11 with ethyl diazoacetate yielded new lambda5-phosphinine 14.     

Architecture of Platonic and Archimedean polyhedral links

A new methodology for understanding the construction of polyhedral links has been developed on the basis of the Platonic and Archimedean solids by using our method of the ‘three-cross-curve and dou- ble-twist-line covering’. There are five classes of polyhedral links that can be explored: the tetrahedral and truncated tetrahedral links; the hexahedral and truncated hexahedral links; the dodecahedral and truncated dodecahedral links; the truncated octahedral and icosahedral links. Our results show that the tetrahedral and truncated tetrahedral links have T symmetry; the hexahedral and truncated hexahedral links, as well as the truncated octahedral links, O symmetry; the dodecahedral and truncated dodeca- hedral links, as well as the truncated icosahedral links, I symmetry, respectively. This study provides further insight into the molecular design, as well as theoretical characterization, of the DNA and protein catenanes.     

Effect of colloidal nanocatalysis on the metallic nanoparticle shape: the Suzuki reaction

Dominantly tetrahedral shaped poly(vinylpyrrolidone)-platinum (PVP-Pt) nanoparticles are shown to catalyze the Suzuki reaction between phenylboronic acid and iodobenzene but are not as active as the spherical palladium nanoparticles studied previously. The dominantly tetrahedral PVP-Pt nanoparticles (55 +/- 4% regular tetrahedral, 22 +/- 2% distorted tetrahedral, and 23 +/- 2% spherical nanoparticles) are synthesized by using the hydrogen reduction method. The transmission electron microscopy (TEM) results show that a transformation of shape from tetrahedral to spherical Pt nanoparticles takes place 3 h into the first cycle of the reaction. After the first cycle, the spherical nanoparticles have a similar size distribution to that of the tetrahedral nanoparticles before the reaction and the observed shape distribution is 18 +/-6% regular tetrahedral, 28 +/- 5% distorted tetrahedral, and 54 +/- 5% spherical nanoparticles. After the second cycle of the Suzuki reaction, the shape distribution is 13 +/- 5% regular tetrahedral, 24 +/- 5% distorted tetrahedral, and 63 +/- 7% spherical nanoparticles. After the second cycle, the transformed spherical nanoparticles continue to grow, and this could be due to the strong capping action of the higher molecular weight PVP (M(w) = 360 000), which makes the nanoparticles more resistant to aggregation and precipitation, unlike the Pd nanoparticles capped with the lower molecular weight PVP (M(w) = 40 000) used previously. The transformation in shape also occurs when the nanoparticles are refluxed in the presence of the solvent, sodium acetate, and iodobenzene and results in spherical nanoparticles with a similar size distribution to that of the tetrahedral nanoparticles before any perturbations. However, in the presence of phenylboronic acid, the regular tetrahedral nanoparticles remain dominant (51 +/- 6%) and maintain their size. These results support our previous studies in which we proposed that phenylboronic acid binds to the nanoparticle surface and thus acts as a capping agent for the particle and reacts with the iodobenzene. Recycling the nanoparticles results in a drastic reduction of the catalytic activity, and this must be due to the transformation of shape from the dominantly tetrahedral to the larger dominantly spherical nanoparticles. This also supports results in the literature that show that spherical platinum nanoparticles do not catalyze this reaction.     

保护剂对K2PtCl6为前体合成纳米铂形状的影响

纳米粒子的性质不仅受到尺寸的影响，还与其形状密切相关，由于铂在催化及材料等领域中有重要应用，因此化学合成特定形状的纳米铂一直备受关注，具有特定表面结构的纳米粒子对于研究催化活性与表面原子结构的关系具有重要意义，目前立方体形状纳米铂已被合成，但高比例四面体形状纳米铂的合成研究很少有报道，     

New sodalite frameworks; synthetic tugtupite and a beryllosilicate framework with a 3:1 Si:Be ratio

Compounds of the formula Na8[Si(6 +y)Be(y)Al(6 - 2y)O24]X2, with X = Cl and Br, and y = 1, 2 and 3 have been synthesised and structurally characterised by combined powder X-ray and neutron diffraction profile analysis. These materials adopt the sodalite framework (SOD) with the tetrahedral species, BeO4, AlO4 and SiO4, disordered across the framework positions. Na8[Si8Be2Al2O24]Cl2, (y = 2), is a synthetic analogue of the naturally occurring semi-precious gemstone tugtupite, while Na8[Si9Be3O24]X2, X = Cl and Br represents a new tetrahedral framework stoichiometry with a Si ratio Be ratio of 3 ratio 1. Additional characterisation using 29Si MASNMR, IR spectroscopy and high-temperature, neutron diffraction show that the observed structure-property trends found when modelling sodalite materials can be extended to these new framework compositions.     

Synthesis and characterization of a polyoxovanadate cluster representing a new topology

A new type of mixed-valence polyoxoanionic cluster, [V(V)13V(IV)3O42(Cl)]8-, composed of 14 {VO5} square pyramids and 2 {VO4} tetrahedral units, hosting a chloride ion has been synthesized and characterized.     

LiSr2(NCN)I3: the first empty tetrahedral strontium(II) entity coordinated by carbodiimide units but without strontium-strontium bonding

LiSr(2)(NCN)I(3), the first extended compound containing empty tetrahedral Sr(4) entities, is synthesized using a new flux route, and it exhibits two interpenetrating three-dimensional networks made up from Sr tetrahedra capped by NCN(2-) anions on their triangular faces and vertex-sharing LiI(6) octahedra.     

Lithium amidohydridoaluminates

The amidohydridometalates [Li(THF)4][HAl(NPh2)3] (1), [Li(DME)3][HAl(N(CH2Ph)2)3] (2), and [((THF)3Li)-(H2Al(NcHex2)2)].0.5toluene (3.0.5toluene; cHex = C6H11) have been prepared by reaction of the corresponding amines with LiAlH4 in THF. For 2 recrystallization from DME is required to obtain crystals, suitable for X-ray diffraction. The new compounds have been characterized by elemental analyses, IR, NMR, and MS techniques, and X-ray structure analyses. According to this the anions of 1, 2, and 3x0.5toluene possess distorted tetrahedral coordination spheres. In 3x0.5toluene a Li...H contact of 184(4) pm was detected to complete the tetrahedral coordination of the Li+ center.     

Tetrahedral distortion and energetic packing penalty in "zeolite" frameworks: linked phenomena?

We report a computational study on the distortion of SiO4 tetrahedra in zeolite frameworks. For all previously observed frameworks, the tetrahedral mismatch was found to span a narrow range (1.0 x 10(-3) to 2.5 x 10(-2) angstroms2) of values, in contrast to the hypothetical frameworks, which were calculated to have a much wider range of mismatch values. The energy of the frameworks was not found to be a function of the tetrahedral distortion for the previously observed and moderately distorted (tetrahedral mismatch <2.5 x 10(-2) angstroms2) hypothetical frameworks. In contrast, the energy of the bulk of the hypothetical frameworks was shown to be a strong function of the tetrahedral distortion. The fact that the framework energies of some hypothetical frameworks lie much higher than both those of the observed frameworks and the values we would expect from our previously developed topological method (the so-called energetic packing penalty) is explained in terms of the tetrahedral distortion contribution to the framework energy which is negligible for the observed frameworks. Finally, it is hypothesized that the absence of tetrahedral distortion is pivotal for a framework to be experimentally realized, in which case a large fraction of hypothetical frameworks are unrealizable and will forever remain in the realms of the abstract.     

A new enantiopure unsaturated dicarboxylate as a 4-connected unit in a flexible homochiral PtS-type framework

Metal cation mediated chiral ligand transformation of (S)-camphanic acid leads to a new enantiopure unsaturated dicarboxylate that links tetrahedral Zn(2+) sites into 3-D homochiral 4-connected PtS-type framework structures, Zn(tced) (1, H(2)tced=1,2,2-trimethyl-3-cyclopentene-1,3-dicarboxylic acid) and Zn(4)(tced)(4)(4,4'-bipy) (2, 4,4'-bipy=4,4'-bipyridine).     

巯基保护的中空金纳米球

基于全统一模型和密度泛函理论(DFT)计算,我们提出了具有高对称性和稳定性的巯基保护的中空金纳米球Au₆₀(SR)₂₀的原子结构。Au₆₀(SR)₂₀由一个二十面体Au₅₀富勒烯中空笼子(由20个四面体Au₄融合构成)和10个[―RS―Au―SR―]订书针结构组成,并遵循“分离和保护”规则。DFT计算表明,这种空心Au₆₀(SR)₂₀纳米球具有大的带隙(1.3 eV)以及在笼中心的核独立化学位移(NICS)为负值(−5),表明其高度的化学稳定性。此外,四面体Au₄单元中心的NICS值远大于空心笼中心的NICS值,表明Au₆₀(SR)₂₀的总体稳定性可能来自每个四面体Au₄单元的局部稳定性。正的谐波振动频率说明Au₆₀(SR)₂₀纳米球至少是势能表面的局部最小值。另外,我们还通过融合四面体Au₄层设计了双层中空金纳米球,表明调整中空金纳米球壳层厚度是可行的。最后,我们还介绍了更大的中空金纳米球Au₁₈₀(SR)₆₀的设计。这项工作提供了可控设计中空金纳米球的新策略。     

Genetic training of network using chaos concept: application to QSAR studies of vibration modes of tetrahedral halides

The chaotic dynamical system is introduced in genetic algorithm to train ANN to formulate the CGANN algorithm. Logistic mapping as one of the most important chaotic dynamic mappings provides each new generation a high chance to hold GA's population diversity. This enhances the ability to overcome overfitting in training an ANN. The proposed CGANN has been used for QSAR studies to predict the tetrahedral modes (nu(1)(A1) and nu(2)(E)) of halides [MX(4)](epsilon). The frequencies predicted by QSAR were compared with those calculated by quantum chemistry methods including PM3, AM1, and MNDO/d. The possibility of improving the predictive ability of QSAR by including quantum chemistry parameters as feature variables has been investigated using tetrahedral tetrahalide examples.     

A tetrahedral coordination compound for second-order nonlinear optics: synthesis,crystal structure and SHG of Zn(2-NH2py)2Cl2

A coordination compound with a tetrahedral molecular configuration, Zn(NH₂py)₂Cl₂(2-NH₂py=2-aminopyridine), was prepared. It is transparent in the visible region and shows second harmonic generation (SHG) effect 8.0 times as strong as that of KDP. X-ray single crystal structure analysis reveals that all Zn(NH₂py)₂Cl₂ molecules are aligned in a fully parallel direction. The advantages and disadvantages of tetrahedral zinc coordination compounds as nonlinear optical (NLO) materials are discussed. The results may represent a novel strategy for designing a new class of transparent NLO materials.     

Tetravalent silicon connectors MenSi(p-C6H4CO2H)(4-n) (n = 0, 1, 2) for the construction of metal-organic frameworks

A series of silicon-centered connecting units, Me(n)Si(p-C6H4CO2H)(4-n) (n = 0, 1, 2), have been prepared and their coordination polymers with Zn(II) metal atoms studied. The tetra-acid L1 (n = 0) acts as a tetrahedral node and reacts with Zn(II) centers to give 1, a novel interpenetrating 3D network containing distorted tetrahedral bimetallic secondary building units (SBUs). The triacid L2 (n = 1) acts as a trigonal pyramidal node and forms an intercalated 2D layered network, 2, with Zn(II) ions, containing distorted octahedral tetranuclear SBUs. Last, the bent diacid L3 (n = 2) reacts with Zn(II) centers to give 3, a corrugated 2D layered structure containing 1D zinc hydroxo chains. Together these three new coordination polymers demonstrate the potential versatility of tetravalent silicon containing connecting ligands for metal-organic framework construction.     

一种直接混合生成Al13硫酸盐晶体的简易方法

将一定量的Na₂SO₄溶液直接加入在60～80 ℃温度下预处理过的Al₁₃溶液中，然后室温陈化12 h，可简便快速地制备具有四面体形貌和纤维状形貌的Al₁₃基硫酸盐晶体。所得晶体的SEM和OS图显示：用本文报道的方法合成的四面体形貌的硫酸盐晶体尺寸大小在150～200 μm，而通过滴定方法的却只有15～25 μm；纤维状的硫酸盐晶体的长径尺度分别是>1 000 μm和0.5～1 μm。对四面体形貌的Al_13<     

Enantioseparation of novel chiral heterometal tetrahedral clusters by high-performance liquid chromatography

A series of novel chiral heterometal tetrahedral clusters have firstly been separated on cellulose tris-(3,5-dimethylphenylcarbamate) stationary phase by high-performance liquid chromatography using n-hexane as the mobile phase containing different alcohols as modifiers. The effects of concentration and structures of alcohols in the mobile phases and structures of chiral heterometal tetrahedral clusters on enantioseparation were investigated. The results showed that the concentration and structures of alcohols had large effects on enantioseparation. It also was found that both the metal in the tetrahedral core and the ligand coordinated to the atom in tetrahedral core had significant effects on their chromatographic behavior.